Arylethyl (= Phenylethanoid) Glycosides and Oligosaccharide from the Stem of Cistanche tubulosa

Three new analogues of the arylethyl (= phenylethanoid) glycoside echinacoside ( 5 ), namely cistantubulosides A ( 1 ), B₁/B₂ ( 2a / 2b ), and C₁/C₂ ( 3a / 3b ), and one new oligosaccharide, cistantubulose A₁/A₂ ( 4a / 4b ), were isolated from the stems of Cistanche tubulosa (Schenk ) R. Wight , together with five known compounds, i.e., campneoside I, campneoside II ( 6 ), echinacoside ( 5 ), tubuloside, and cistanoside F. Among the compounds isolated, 2a / 2b, 3a / 3b, 4a / 4b , campneoside I, campneoside II ( 6 ), and cistanoside F each consisted of a pair of epimers. The structures of the new compounds were elucidated on the basis of spectral data.     

Rotundifolides A and B,Two New Enol‐Derived Butenolactones from the Bark of Litsea rotundifolia var. oblongifolia

Two new enol‐derived butenolactones, rotundifolides A ( 1 ) and B ( 2 ), along with four known related compounds, lincomolide C ( 3 ), lincomolide A ( 4 ), marliolide ( 5 ), and litsenolide A₁ ( 6 ), were isolated from the bark of Litsea rotundifolia var. oblongifolia. The structures of the new metabolites were characterized by spectroscopic methods and comparison with known compounds.     

New Diterpenoid Alkaloids from Aconitum liangshanicum

One new C₁₉‐diterpenoid alkaloid, named liangshantine ( 1 ), and three new C₂₀‐diterpenoid alkaloids, liangshansines A–C ( 2 – 4 , resp.), as well as eight known compounds, were isolated from the roots of Aconitum liangshanicum. The structures of these new alkaloids were elucidated by spectroscopic methods.     

New C19－Diterpenoid Alkaloids from the Roots of Delphinium Giraldii

Three new C19-diterpenoid alkaloids, giraldines A (1), B (3) and C (4), were isolated from the roots of Delphinium giraldii Diels, together with three known C19-diterpenoid alkaloids, dihydrogadesine (5), tatsiensine (6) and siwanine A (7), as well as their structures were elucidated by chemical evidence and spectral analyses, including IR, MS, 1D NMR and 2D NMR.     

New Diterpene Alkaloids from Aconitum sungpanense var. leucanthum

Five new C₁₉ diterpene alkaloids, leucanthumsines A ( 1 ), B ( 2 ), C ( 3 ), D ( 4 ), and E ( 5 ), were isolated from the Chinese medicinal herb Aconitum sungpanense var. leucanthum, together with the known C₁₉ diterpene alkaloids pseudaconine, neoline, 1‐O‐methyldelphisine, crassicaudine, chasmanine, talatisamine, indaconitine, ezochansmanine, and leueantine D. The structures of these new alkaloids were elucidated by HR‐MS and advanced NMR methods, including ¹H‐ and ¹³C‐NMR (DEPT), ¹H,¹H‐COSY, HMQC, and HMBC experiments.     

A New Ketone and a Known Anticancer Triterpenoid from the Leaves of Onosma limitaneum

A new ketone, onosmone ( 1 ), and a known anticancer triterpenoid, bauerenone, besides β‐sitosterol glycoside were isolated for the first time from the CHCl₃ extract of the leaves of Onosma limitaneum. The structures of these compounds were established on the basis of spectral and chemical evidence.     

Macrocyclic Pyrrolizidine Alkaloids and Silphiperfolanol Angelate Esters from Solanecio mannii

Three new compounds, the silphiperfolanol angelate ester umutagarananol ( 1 ), the macrocyclic pyrrolizidine alkaloids umutagarinine A and B ( 2 – 3 ), and five known secondary metabolites ( 4 – 8 ) were isolated from the CH₂Cl₂−MeOH (1 : 1) extract of the roots and the stem bark of Solanecio mannii (Hook. f.) (Asteraceae). The isolated compounds were characterized by NMR and IR spectroscopic, and mass spectrometric analyses, whereas the relative stereochemistry of 4 was established by NAMFIS-based combined computational and solution NMR analysis. Synthetic modification of 5 provided two new compounds, 2-angeloyloxy-4,8-epoxypresilphiperfolane ( 9 ) and 2-angeloyloxy-4,8-epoxypresilphi-perfolane ( 10 ). The crude extracts and the isolated constituents showed weak antibacterial activities (EC₅₀ 0.7–13.3 mM) against the Gram-negative Escherichia coli and the Gram-positive Bacillus subtilis. Compounds 2 , 3 and 4 exhibited strong cytotoxicity against MCF-7 human breast cancer cells, with EC₅₀ values of 35.6, 21.7 and 12.5 μM, respectively.     

Three New Chromanones from Calea clausseniana

Three new chromanones, uniflorol A acetate ( 1 ), uniflorol B acetate ( 2 ), and 2,2‐dimethyl‐6‐{1‐[(4′‐acetoxy)angeloyloxy]ethyl}chroman‐4‐one ( 3 ), together with the known chromanone 4 , and two known p‐hydroxyacetophenone derivatives, 5 and 6 , were isolated from the CH₂Cl₂ crude extract of the underground parts of Calea clausseniana Baker . The structures of the new compounds were elucidated by spectroscopic analyses, including 2D‐NMR techniques.     

Chemical Constituents from the Bark of Garcinia xanthochymus and Their 1,1‐Diphenyl‐2‐picrylhydrazyl (DPPH) Radical‐Scavenging Activities

A new bis‐xanthone (xanthone=9H‐xanthen‐9‐one), named bigarcinenone A ( 1 ) which is the first example of a bis‐xanthone with the xanthone–xanthone linkage between an aromatic C‐atom and a C₅ side chain from a guttiferae plant, a new phloroglucinol (=benzene‐1,3,5‐triol) derivative, named garcinenone F ( 2 ), together with seven known xanthones were isolated from the bark of Garcinia xanthochymus. Their structures were elucidated by spectroscopic methods, especially 2D‐NMR techniques. Bigarcinenone A ( 1 ) exhibited potent antioxidant activity in the 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) radical‐scavenging test with a IC₅₀ value of 9.2 μM , compared to the positive control, the well‐known antioxidant butylated hydroxytoluene (BHT) with a IC₅₀ of 20 μM (Table 3).     

Rare C25 Steroids Produced by Penicillium chrysogenum P1X,a Fungal Endophyte of Huperzia serrata

Three new metabolites, norcyclocitrinol A ( 1 ), erythro‐11α‐hydroxyneocyclocitrinol ( 2 ), and pesudocyclocitrinol A ( 3 ), along with six known analogs, i.e., neocyclocitrinols A–D ( 4 – 7 , resp.), cyclocitrinol ( 8 ), and 24‐epicyclocitrinol ( 9 ), were isolated and identified from the culture broth of Penicillium chrysogenum P1X, a fungal endophyte of Huperzia serrata. Compounds 1 – 9 were identified by spectroscopic methods to share the same C₂₅‐steroid skeleton featuring an unusual bicyclo[4.4.1] A/B ring system. In particular, 1 represents the first example of a C₂₅ steroid with a bisnor C‐atom side chain. All compounds were evaluated for their cytotoxic activities against HeLa and HepG2 cell lines. However, none of them exhibited a significant cytotoxicity at a concentration of 20 μM .     

Chromenone Glucosides Acylated with Monoterpene Acids from the Leaves of Eucalyptus camaldulensis var. obtusa

Three new chromenone glucosides acylated with monoterpene acids, eucamaldusides A ( 1 ), B ( 2 ), and C ( 3 ), were isolated from the leaves of Eucalyptus camaldulensis var. obtusa, together with the five known compounds ursolic acid lactone, obtusilin, β‐sitosterol glucoside, 4‐hydroxybenzoic acid, and cypellocarpin C. The structures of the new compounds were established by exhaustive 1D‐ and 2D‐NMR spectroscopic studies. Their configuration was determined by measuring the [α]_D of the known methyl esters of the monoterpene acids obtained by methanolysis of 1 – 3 .     

Two New Cytotoxic Spirostane‐Steroidal Saponins from the Roots of Bletilla striata

Two new spirostane‐steroidal saponins, bletilnoside A ( 1 ) and bletilnoside B ( 2 ), together with five known compounds, 3 – 7 , were isolated from the roots of Bletilla striata (Thunb .) Reichb . F. The structures of the new compounds were determined based on their 1D‐ and 2D‐NMR spectral data. The isolated compounds 1 – 7 were tested for cytotoxicity against four human tumor cells (A549, SK‐OV‐3, SK‐MEL‐2, and HCT15) in vitro using a sulforhodamin B bioassay, and compounds 1, 2 , and 5 showed significant cytotoxicities against all tested tumor cell lines with IC₅₀ values ranging from 3.98±0.16 to 12.10±0.40 μM .     

The glycosides of Marsdenia erecta R. Br. I. Isolation, glycoside and aglycone. 325

Dried leaves of Marsdenia erecta R. Br. gave over 6% of a crude glycoside mixture, the main portion of which consisted of weakly polar material, soluble in ether or chloroform. By mild acid hydrolysis it yielded crude sugars and aglycones. The following four crist. sugars were isolated: D -cymarose, D -oleandrose and two bioses: pachybiose and marsectobiose (C₁₄H₂₄O₈, new). By PC. and TLC. the presence of digitoxose, canarose, thevetose and 3-O-methyl-6-deoxyallose could be demonstrated. The crude acyl-genin mixture contained β-sitosteryl-β-D -glucopyranoside and three highly hydroxylated pregnane derivatives: drevogenin-P, 17 β-marsdenin (C₂₁H₃₂O₆, new) and marsectohexol (C₂₁H₃₄O₆, new), all partly esterified with acetic, tiglic and benzoic acid. Five crist. acyl-genins (A1–A5) were isolated by chromatography, but most of them still were mixtures. After alkaline hydrolysis of the crude acyl-genins 6 acyl-free compounds were obtained. 4 of them were identical with the above mentioned substances, the other two: 17-iso-drevogenin-P and marsdenin (17 α-marsdenin) are formed from drevogenin-P and 17 β-marsdenin by isomerisation.     

New Alkaloids from Aconitum vaginatum

Two new amide alkaloids, vaginatunine A and B ( 1 and 2 , resp.), and a new C₁₈‐diterpenoid alkaloid vaginatunine C ( 3 ), together with four known alkaloids, were isolated from the tubers of Aconitum vaginatum. Their structures were determined by means of spectroscopic analyses and comparison of the data with those reported previously.     

Seco‐Tremulanes from Cultures of the Basidiomycete Flavodon flavus BCC 17421

A new seco‐tremulane, 11,12‐epoxy‐5,6‐secotremula‐1,6(13)‐dien‐5,12‐olide ( 1 ), was isolated together with the known compounds, conocenolides A ( 2 ) and B ( 3 ), tremulenediol A ( 4 ), tremulenolide A ( 5 ), and two lanostane triterpenoids, trametenolic acid B ( 6 ), and pinicolic acid A ( 7 ), from cultures of the basidiomycete Flavodon flavus BCC 17421. Interconversion of conocenolides A/B was demonstrated. Compound 1 exhibited weak cytotoxic activities, whereas tremulenediol A showed antiplasmodial activity (IC₅₀ 8.6 μg/ml). Pinicolic acid A exhibited activity against herpes simplex virus type‐1 (IC₅₀ 15 μg/ml) as well as cytotoxic activities.     

Three New Eudesmanolactones (=Eudesmanolides) from Camchaya loloana

Three new eudesmanolactones (=eudesmanolides), loloanolide A ( 1 ), loloanolide B ( 2 ), and 1‐O‐acetylloloanolide B ( 3 ), together with five known compounds, were isolated from the CHCl₃ extract of the aerial parts of Camchaya loloana. Their structures were elucidated on the basis of spectroscopic analysis. This type of eudesmanolactones bearing a 2‐(hydroxymethyl)acryloyloxy group at C(8) was discovered for the first time. Compounds 1 – 3 exhibited cytotoxicity against the HepG2 cell line, with GI₅₀ values of 22.9, 18.1, and 12.8 nmol/ml, respectively.     

Lycopodium Alkaloids from Huperzia serrata

Three new lycopodium alkaloids, huperserramines A–C ( 1 – 3 , resp.), along with 15 known ones, lycopodine‐6α,11α‐diol ( 4 ), lycoposerramine H ( 5 ), lycoposerramine I ( 6 ), lycopodine‐6α‐ol ( 7 ), lycoposerramine M ( 8 ), diphaladine A ( 9 ), lycoposerramine K ( 10 ), lycoposerramine W ( 11 ), huperzine M ( 12 ), luciduline ( 13 ), phlegmariuine N ( 14 ), huperzine A ( 15 ), huperzine B ( 16 ), lycodine ( 17 ), and lycoposerramine R ( 18 ), were isolated from the whole plant of Huperzia serrata. Their structures were established by spectroscopic methods, including 2D‐NMR and MS analyses. All the isolates were evaluated for their inhibitory effects on acetylcholinesterase (AChE) and α‐glucosidase. As a result, lycopodine‐6α,11α‐diol ( 4 ) exhibited more potent α‐glucosidase inhibitory activity (IC₅₀ 148±5.5 μM ) than the positive control acarbose (IC₅₀ 376.3±2.7 μM ).     

New Steroids and a New Alkaloid from the Gorgonian Isis minorbrachyblasta: Structures,Cytotoxicity, and Antilarval Activity

Two new polyoxygenated steroids, (1α,3β,7α,11α,12β)‐gorgost‐5‐ene‐1,3,7,11,12‐pentol 12‐acetate ( 1 ) and 11‐O‐acetyl‐22‐epihippuristanol ( 2 ), and a new alkaloid, 2,3,5,6,11,11b‐hexahydro‐2‐hydroxy‐1H‐indolizino[8,7‐b]indole‐2‐carboxylic acid ( 3 ), together with three known compounds, 22‐epihippuristanol ( 4 ), hippuristanol ( 5 ), and tryptamine ( 6 ), were isolated from the EtOH/CH₂Cl₂ extracts of the South China Sea gorgonian Isis minorbrachyblasta. The structures of the new compounds were determined by spectroscopic methods. Compound 1 showed weak cytotoxicity against A549, HONE1, and HeLa cancer cell lines and strong antilarval activity towards Bugula neritina larvae with an EC₅₀ value of 5.8 μg/ml. Compound 5 showed moderate cytotoxicity against A549, HONE1, and HeLa cell lines, and the epimer mixture 4 / 5 (weight ratio 3 : 2) exhibited potent cytotoxicity against A549 and HONE1 cell lines with IC₅₀ values of 4.2 and 4.8 μg/ml, which indicated that epimers 4 and 5 might have a synergistic effect on their cytotoxicity against A549 and HONE1 cell lines.     

Bioactive Cytochalasins from Aspergillus flavipes,an Endophytic Fungus Associated with the Mangrove Plant Acanthus ilicifolius

Five new cytochalasins, Z₁₆–Z₂₀ ( 1 – 5 ), and three known ones, 6 – 8 , were isolated from Aspergillus flavipes, an endophytic fungus associated with Acanthus ilicifolius. Their structures were elucidated on the basis of comprehensive spectral analysis. Cytochalasin Z₁₇ ( 2 ) and rosellichalasin ( 8 ) showed cytotoxic activities against A‐549 cell lines with IC₅₀ values of 5.6 and 7.9 μM , respectively.     

Three New Homologous 3‐Alkyl‐1,4‐benzoquinones from the Fruiting Bodies of Daldinia concentrica

A new homologous series of 3‐alkyl‐5‐methoxy‐2‐methyl‐1,4‐benzoquinones ( 1 – 3 ), with chain lengths of C₂₁ to C₂₃, were isolated from the fruiting bodies of Daldinia concentrica, together with five known compounds. The molecular structures were established by spectroscopic methods.